EP0632002B1 - Nicht-azeotropische Difluoromethan und 1,1,1,2-Tetrafluoroethan enthaltende Zusammensetzungen und ihre Verwendung als Kühlflüssigkeiten für Klimaanlagen - Google Patents

Nicht-azeotropische Difluoromethan und 1,1,1,2-Tetrafluoroethan enthaltende Zusammensetzungen und ihre Verwendung als Kühlflüssigkeiten für Klimaanlagen Download PDF

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Publication number
EP0632002B1
EP0632002B1 EP94401394A EP94401394A EP0632002B1 EP 0632002 B1 EP0632002 B1 EP 0632002B1 EP 94401394 A EP94401394 A EP 94401394A EP 94401394 A EP94401394 A EP 94401394A EP 0632002 B1 EP0632002 B1 EP 0632002B1
Authority
EP
European Patent Office
Prior art keywords
hfc
air conditioning
tetrafluoroethane
hcfc
mixtures containing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94401394A
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English (en)
French (fr)
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EP0632002A1 (de
Inventor
Sylvie Macaudiere
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Elf Atochem SA
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Filing date
Publication date
Application filed by Elf Atochem SA filed Critical Elf Atochem SA
Publication of EP0632002A1 publication Critical patent/EP0632002A1/de
Application granted granted Critical
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Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/128—Perfluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/05—Use of one or more blowing agents together

Definitions

  • the present invention relates to the field of refrigeration and more particularly relates to non-azeotropic mixtures of refrigerants having no or little action on the environment, to replace chlorofluorocarbons (CFCs) or hydrochlorofluorocarbons (HCFCs) in air conditioning systems.
  • CFCs chlorofluorocarbons
  • HCFCs hydrochlorofluorocarbons
  • thermodynamic cycle generally defined by an evaporation temperature between 0 and 10 ° C (most often 7 ° C), a condensation temperature between + 30 and 55 ° C, liquid sub-cooling of the order of - 5 ° C and overheating of the vapors by at least 10 ° C.
  • HCFC 22 chlorodifluoromethane
  • thermodynamic properties in particular a coefficient of performance (COP) and cooling capacity, as close as possible to that of HCFC 22.
  • the discharge temperature does not exceed that of HCFC 22 by more than about 5 ° C.
  • the substitute must be non-flammable and remain so in the event of a vapor phase leak.
  • HFC 32 Difluoromethane (HFC 32), tetrafluoromethane (FC 14), octafluoropropane (FC 218) and 1,1,1,2-tetrafluoroethane (HFC 134a) have no action on ozone compared to chlorinated compounds. very little impact on the environment.
  • HFC 32 has the major drawback of being flammable. Furthermore, its boiling point which is much lower than that of HCFC 22 means that it is not suitable for the direct replacement of HCFC 22. It is known to those skilled in the art that a low boiling point causes very high pressures which make it impossible to use such a fluid in existing systems for safety reasons.
  • HFC 134a a non-flammable compound, is a good refrigerant in terms of efficiency, but its too low cooling capacity makes it impossible to use as a substitute for HCFC 22.
  • the mixtures according to the invention can therefore be used in air conditioning systems, in particular for replacing HCFC 22.
  • a very particularly preferred mixture contains approximately 32% of HFC 32, 65% of HFC 134a and 3% of FC 218.
  • This example shows the evolution of the pressure and of the composition of a HFC 32 / HFC 134a / FC 218 mixture, during a vapor phase leak.
  • the temperature was kept constant at 24 ° C.
  • the pressures were measured using a Heise pressure gauge with an accuracy greater than ⁇ 1%.
  • the container is initially loaded with approximately 342 g of a mixture containing by mass 33% of HFC 32, 64% of HFC 134a and 3% of FC 218.
  • the maximum admissible values of HFC 32 so that the mixtures remain non-flammable at room temperature in mixtures 32 / 134a and 32/218 are 56% by weight and 67% by weight respectively.
  • the ternary mixtures according to the invention are therefore non-flammable and remain so even during a vapor leak since the maximum content of HFC 32 is 47.6%.
  • Table 2 collates the data for a mixture containing by mass 33% of HFC 32, 64% of HFC 134a and 3% of FC 218. TABLE 2 Temperature (° C) Absolute pressure (bar) Mix 32 / 134a / 218 HCFC 22 -30 1.75 1.63 -15 3.38 2.96 0 5.61 4.98 15 8.82 7.89 30 13.32 11.92 45 19.34 17.29 60 27.10 24.26
  • This example illustrates the use of the mixtures according to the invention as refrigerants.
  • thermodynamic performances of different ternary mixtures according to the invention were compared with the performances of the constituents alone, with those of their binary mixtures and with those of HCFC 22 for a standard thermodynamic cycle defined as follows: Condensation temperature + 43 ° C Evaporation temperature + 7 ° C Liquid sub-cooling - 5 ° C Overheating of vapors + 11 ° C
  • Table 3 summarizes the thermodynamic performances observed under these conditions for HFC 32, FC 218, HFC 134a and their mixtures.
  • TABLE 3 Composition (mass%) HFC 32 / HFC 134a / FC 218 Temperature shift ° C COP * Volumetric refrigeration capacity * Discharge temperature difference * ° C Condensation pressure difference * bar 100/0/0 0 0.933 1.57 + 17 + 10.3 0/100/0 0 1.021 0.66 - 14 - 5.5 0/0/100 0 0.880 0.67 - 27 - 2.5 25/75/0 5.8 0.979 0.89 - 5 - 1.3 30/70/0 6.2 0.974 0.93 - 3 - 0.5 35/65/0 6.5 0.969 0.98 - 2 - 0.3 38/0/62 0 0.802 1.42 - 8 + 14.5 0/25/75 0 0.897 0.80 - 23 - 0.5 0/70/30 9.2 0.952 0.75 - 17

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)

Claims (4)

  1. Nichtazeotrope Mischung, enthaltend in Masse 26 bis 34 % Difluormethan, 56 bis 73 % 1,1,1,2,-Tetrafluorethan und 1 bis 10% Tetrafluormethan oder Octafluorpropan.
  2. Mischung nach Anspruch 1, enthaltend in Masse 26 bis 34 % Difluormethan, 56 bis 73 % 1,1,1,2-Tetrafluorethan und 1 bis 10 % Octafluorpropan.
  3. Mischung nach Anspruch 2, enthaltend in Masse etwa 32 % Difluormethan, 65 % 1,1,1,2-Tetrafluorethan und 3 % Octafluorpropan.
  4. Verwendung einer Mischung nach einem der Ansprüche 1 bis 3 als Kühlmittelflüssigkeit für die Luftklimatisierung.
EP94401394A 1993-06-30 1994-06-22 Nicht-azeotropische Difluoromethan und 1,1,1,2-Tetrafluoroethan enthaltende Zusammensetzungen und ihre Verwendung als Kühlflüssigkeiten für Klimaanlagen Expired - Lifetime EP0632002B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9307975 1993-06-30
FR9307975A FR2707629B1 (fr) 1993-06-30 1993-06-30 Mélanges non azéotropiques contenant du difluorométhane et du 1,1,1,2-tétrafluoroéthane et leurs applications comme fluides frigorigènes en conditionnement d'air.

Publications (2)

Publication Number Publication Date
EP0632002A1 EP0632002A1 (de) 1995-01-04
EP0632002B1 true EP0632002B1 (de) 1997-06-04

Family

ID=9448730

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94401394A Expired - Lifetime EP0632002B1 (de) 1993-06-30 1994-06-22 Nicht-azeotropische Difluoromethan und 1,1,1,2-Tetrafluoroethan enthaltende Zusammensetzungen und ihre Verwendung als Kühlflüssigkeiten für Klimaanlagen

Country Status (8)

Country Link
US (1) US5538660A (de)
EP (1) EP0632002B1 (de)
JP (1) JP2698319B2 (de)
KR (1) KR0133461B1 (de)
AU (1) AU663996B2 (de)
DE (1) DE69403562T2 (de)
ES (1) ES2102163T3 (de)
FR (1) FR2707629B1 (de)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2722794B3 (fr) * 1994-07-19 1996-09-13 Atochem Elf Sa Melanges non azeotropiques de difluoromethane, trifluoromethane et 1,1,1,2-tetrafluoroethane, et leur application comme fluides frigorigenes
GB9522701D0 (en) * 1995-11-07 1996-01-10 Star Refrigeration Centrifugal compression refrigerant composition
US6173577B1 (en) 1996-08-16 2001-01-16 American Superconductor Corporation Methods and apparatus for cooling systems for cryogenic power conversion electronics
US6023934A (en) * 1996-08-16 2000-02-15 American Superconductor Corp. Methods and apparatus for cooling systems for cryogenic power conversion electronics
GB9618207D0 (en) * 1996-08-30 1996-10-09 Ici Plc Refrigerant compositions
US5801937A (en) * 1996-10-16 1998-09-01 American Superconductor Corporation Uninterruptible power supplies having cooled components
KR100405189B1 (ko) 2001-02-16 2003-11-12 한국과학기술연구원 혼합냉매 조성물
US20030057396A1 (en) * 2001-09-25 2003-03-27 Cawley Richard E. Replacement refrigerant for R410A
US6841087B2 (en) 2002-04-19 2005-01-11 Korea Institute Of Science And Technology Refrigerant composition comprising difluoromethane, 1,1,1-trifluoroethane and 1,1,1,2-tetrafluoroethane
US6821583B2 (en) 2002-07-03 2004-11-23 Kodak Polychrome Graphics Llc Imageable element for single fluid ink
US6800216B2 (en) 2002-07-24 2004-10-05 Korea Institute Of Science And Technology Refrigerant composition for replacing chlorodifluoromethane
US6776922B2 (en) * 2002-07-24 2004-08-17 Korea Institute Of Science And Technology Refrigerant composition comprising difluoromethane, 1,1,1-trifluoroethane and 1,1-difluoroethane
JP5572284B2 (ja) * 2007-02-27 2014-08-13 Ｊｘ日鉱日石エネルギー株式会社 冷凍機油および冷凍機用作動流体組成物
CN111592858B (zh) * 2020-05-21 2022-01-11 冰山松洋生物科技(大连)有限公司 混合制冷剂、制冷系统及制冷装置

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA705327A (en) * 1965-03-09 Allied Chemical Corporation Compositions of fluorocarbons
US4810403A (en) * 1987-06-09 1989-03-07 E. I. Du Pont De Nemours And Company Halocarbon blends for refrigerant use
GB2244492B (en) * 1989-09-12 1993-08-04 Star Refrigeration Three-component refrigerant mixture
EP0430169B1 (de) * 1989-11-30 1994-08-17 Matsushita Electric Industrial Co., Ltd. Arbeitsmittel
EP0430171B1 (de) * 1989-11-30 1993-10-06 Matsushita Electric Industrial Co., Ltd. Arbeitsmittel
CN1029625C (zh) * 1990-12-17 1995-08-30 纳幕尔杜邦公司 氟化烃的恒沸组合物
WO1992016597A1 (en) * 1991-03-18 1992-10-01 Allied-Signal Inc. Non-azeotropic refrigerant compositions comprising difluoromethane; 1,1,1-trifluoroethane; or propane
GB9108527D0 (en) * 1991-04-18 1991-06-05 Ici Plc Refrigerant compositions
JPH0517753A (ja) * 1991-07-12 1993-01-26 Matsushita Electric Ind Co Ltd 作動流体
JPH0585967A (ja) * 1991-09-26 1993-04-06 Daikin Ind Ltd フルオロアルカン混合物
US5290466A (en) * 1991-10-31 1994-03-01 E. I. Du Pont De Nemours And Company Compositions of difluoromethane and tetrafluoroethane
US5294359A (en) * 1992-02-03 1994-03-15 Alliedsignal Inc. Refrigerant compositions
JPH0665561A (ja) * 1992-08-20 1994-03-08 Matsushita Electric Ind Co Ltd 作動流体
US5387357A (en) * 1992-09-25 1995-02-07 E. I. Du Pont De Nemours And Company Azeotropic or azeotrope-like compositions of ammonia and hydrofluorocarbons
JPH06212148A (ja) * 1993-01-20 1994-08-02 Showa Denko Kk 冷媒組成物

Also Published As

Publication number Publication date
DE69403562D1 (de) 1997-07-10
EP0632002A1 (de) 1995-01-04
KR950000830A (ko) 1995-01-03
FR2707629A1 (fr) 1995-01-20
US5538660A (en) 1996-07-23
AU663996B2 (en) 1995-10-26
JPH0753419A (ja) 1995-02-28
DE69403562T2 (de) 1997-11-13
FR2707629B1 (fr) 1995-09-01
AU6606394A (en) 1995-02-02
KR0133461B1 (ko) 1998-04-20
JP2698319B2 (ja) 1998-01-19
ES2102163T3 (es) 1997-07-16

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